The present invention relates to a thermosetting powder coating composition. Particularly the present invention relates to a thermosetting powder coating composition which is less affected by mixing of other powder coating composition at coating.
Powder coating compositions containing a fluorine-containing resin are known in various patent publications such as JP -B-6-104792, JP-A-1-103670 and JP-A-8-41131, and can give a coated article being excellent in weather resistance and having a good appearance.
In an actual coating site of a powder coating, from the viewpoint of productivity, coating and baking of plural powder coatings are carried out on one coating line, and operation of the line is changed over for each powder coating.
However only by mixing of a small amount of the powder coating containing a fluorine-containing resin to other resin powder coating, various defects arise on a coating film of the other resin. This is one of the reasons why fluorine-containing resin-based powder coatings are not spread on the market irrespective of excellent physical properties of a coating film thereof.
The present inventors have continued their studies to find out a fluorine-containing resin powder coating composition which is less affected by mixing of other coating composition on a coating line and have found that the above-mentioned defects attributes to miscibility of a fluorine-containing resin with other resin and further that a fluorine-containing copolymer featured by insolubility in tetrahydrofuran (THF) can solve the above-mentioned problem. Thus the present invention was completed.
Namely the present invention relates to the thermosetting powder coating composition characterized in that the composition comprises (A) a fluorine-containing copolymer having crosslinkable functional group and (B) a curing agent and that the fluorine-containing copolymer (A) has a perfluoroolefin unit, has a fluorine content of not less than 10% by weight and is not dissolved in THF substantially.
It is preferable that the fluorine-containing copolymer (A) having crosslinkable functional group has a melting point of not more than 160xc2x0 C. and a melt flow rate (MFR) of from 1 to 1,000 g/10 min when measured at 130xc2x0 C. at a load of 2.1 kg.
Examples of the preferred fluorine-containing copolymer (A) having crosslinkable functional group are those comprising tetrafluoroethylene (TFE), hexafluoropropylene (HFP), ethylene (ET) and monomer unit having crosslinkable functional group and being copolymerizable therewith or those comprising TFE, HFP, isobutylene (IB) and monomer unit having crosslinkable functional group and being copolymerizable therewith.
Example of the preferred crosslinkable functional group is at least one of hydroxyl, carboxyl and epoxy.
Further it is preferable to introduce a vinyl ester compound unit, for example, vinyl benzoate unit and/or vinyl pivalate unit as a unit constituting the copolymer (A).
The present invention also relates to a coated article obtained by coating the above-mentioned thermosetting powder coating composition to a substrate and then baking it.
First the fluorine-containing copolymer (A) having crosslinkable functional group and used in the present invention is explained below.
The fluorine-containing copolymer (A) having crosslinkable functional group is one which has at least the following characteristics (1) to (4).
(1) Having a Perfluoroolefin Unit
Example of perfluoroolefin is, for instance, at least one of perfluoroolefins such as TFE, HFP and perfluoro(vinyl ether). Particularly TFE and HFP are preferred. When the copolymer has a perfluoroolefin unit, a coating film being excellent in weather resistance, water resistance and stain-proofing property can be obtained. It is preferable that the perfluoroolefin unit is contained in the copolymer in an amount of not less than 5% by mole, especially 10 to 95% by mole.
(2) Having a Fluorine Content of Not Less Than 10% by Weight
The fluorine content derives from the perfluoroolefin unit and/or other fluorine-containing monomer. The fluorine content is not less than 10% by weight, preferably 20 to 75% by weight for the same reason as in (1) above.
Examples of the other fluorine-containing monomer are, for instance, vinylidene fluoride, trifluoroethylene, monofluoroethylene, chlorotrifluoroethylene, and the like. Those other fluorine-containing monomer units are optional units. A content thereof is not more than 30% by mole, usually 0 to 10% by mole.
(3) Being Insoluble in THF Substantially
Being insoluble in THF means being inferior in compatibility with a resin soluble in THF. Namely when after coating of a powder coating of a resin soluble in THF, the powder coating of the present invention is coated on the same coating line, or when carrying out coating in the reverse order, the fluorine-containing copolymer (A) is less affected by other resin, and the influence of mixing of the fluorine -containing copolymer (A) on the other powder coating can be decreased.
Being insoluble substantially encompasses the case of being soluble in THF in a concentration of less than 0.5% by weight. This is because when substantially measuring an intrinsic viscosity [xcex7] of the resin in THF solution, a reliable intrinsic viscosity [xcex7] cannot be measured unless the copolymer has a solubility of about 0.5% by weight or more.
Examples of the resin which is soluble in THF and is used for a powder coating are, for instance, an acrylic resin, polyester resin, epoxy resin, fluorine-containing resin described in JP-B-6-104792, and the like.
(4) Having Crosslinkable Functional Group
The crosslinkable functional group has functions of giving a curing site to the fluorine-containing copolymer (A) and giving a highly hard coating film subjected to thermosetting by a reaction with a curing agent, thus increasing a surface hardness while maintaining good flexibility.
In the present invention, examples of the crosslinkable functional group are, for instance, functional groups represented by the formulae (i): 
wherein R is an alkyl group having 1 to 3 carbon atoms.
Among the above-mentioned functional groups, preferred are those represented by the formulae (ii): 
Examples of the monomer capable of introducing such a functional group are, for instance, perfluorobutenoic acid (PFBA), a fluorine-containing monomer having an ether unit described in JP-A-8-67795 and in addition, non-fluorine-containing monomer having carboxyl such as maleic anhydride (MAL); hydroxyl-containing monomer such as hydroxybutyl vinyl ether (HBVE) and allyl alcohol; epoxy-containing monomer such as glycidyl vinyl ether (GVE); vinylmethoxysilane, vinylethoxysilane, monomer having hydrolyzable silyl group described in JP-A-8-120211, monomer having aminopropoxy group, and the like.
From the viewpoint of reactivity in the baking temperature range in case of combination use with a known curing agent, preferred are PFBA, carboxyl-containing monomer such as maleic anhydride, hydroxyl-containing monomer such as HBVE and glycidyl-containing monomer such as GVE.
The crosslinkable functional group forms a curing site, and its amount varies depending on reactivity of the functional group and kind of a curing agent. It is preferable that based on the whole fluorine-containing resin, an acid value is from 1 to 300 mgKOH/g, a hydroxyl value is from 1 to 200 mgKOH/g or an equivalent of epoxy is from 5 to 15,000 equivalents.
It is further preferable that the copolymer has the following characteristics.
(5) Having a Melting Point of Not More Than 160xc2x0 C.
When the melting point is in this range, a good flow characteristic is given at baking.
(6) MFR Being From 1 to 1,000 g/10 min when Measured at 130xc2x0 C. at a Load of 2.1 kg (The Measuring Conditions are Hereinafter the Same)
MFR is an important factor at melt-kneading or baking, particularly at baking. The larger the MFR is, the more the flowing property of molten resin increases. Therefore a smooth and uniform coating film is easily formed. But on the other hand, dripping easily occurs, and at kneading, shearing is not applied to a kneaded composition and uniform kneading is difficult. There occurs a defect that water resistance and impact resistance of a coating film are lowered. When the MFR is too small, flowability at baking is insufficient and a coating film does not become smooth and uniform. A preferred MFR is from 5 to 100 g/10 min.
From the above-mentioned points of view, a content of the unit giving crosslinkable functional group may be selected in the range of from 0.1 to 30% by mole, especially 1 to 20% by mole based on the fluorine-containing copolymer.
Also when the fluorine-containing copolymer (A) contains a vinyl ester compound unit as a constitutive unit thereof, adhesion of the obtained coating film to a substrate is enhanced, and also compatibility with a curing agent is improved, thus giving a coating film having a high gloss. Examples of the vinyl ester compound are non-fluorine-containing vinyl esters, for instance, vinyl benzoate (VBz), vinyl pivalate (VPi) and a mixture thereof. It is desirable that the vinyl ester compound is introduced in the copolymer (A) in an amount of 0.1 to 25% by mole, preferably 0.5 to 20% by mole.
The fluorine-containing copolymer having crosslinkable functional group can be obtained by copolymerizing each of the above-mentioned monomers. The polymerization may be carried out by usual polymerization methods such as emulsion polymerization, suspension polymerization and solution polymerization. Also a monomer having crosslinkable functional group may be grafted on the copolymer.
Non-restricted examples of the fluorine-containing copolymer having crosslinkable functional group of the present invention are those having the following combinations of monomers and satisfy the requirements (1) to (4) and further preferably (5) and (6).
Non-restricted examples of more concrete copolymer are as follows.
TFE/HFP/ET/PFBA copolymer (mole ratio: 25 to 40/10 to 20/35 to 48/0.1 to 10), TFE/HFP/ET/HBVE copolymer (mole ratio: 25 to 40/10 to 20/35 to 48/0.1 to 10), TFE/HFP/ET/GVE copolymer (mole ratio: 25 to 40/10 to 20/35 to 48/0.1 to 10), TFE/HFP/IB/HBVE copolymer (mole ratio: 25 to 40/10 to 20/35 to 48/0.1 to 10), TFE/HFP/ET/HBVE/VBz copolymer (mole ratio: 25 to 40/10 to 20/35 to 48/0.1 to 10/3 to 8), TFE/HFP/ET/HBVE/VBz/VPi copolymer (mole ratio: 25 to 40/10 to 20/35 to 48/0.1 to 10/3 to 8/3 to 8)
TFE/HFP/ET copolymer described in JP-A-8-41131 does not have functional group and does not satisfy the Requirement (4). A fluorine-containing copolymer (JP-A-9-165535) mainly comprising vinylidene fluoride (VdF) does not satisfy insolubility in THF (Requirement (3)).
It is preferable that the fluorine-containing copolymer having crosslinkable functional group and used in the present invention further has the following physical property.
Glass transition temperature (Tg): It is preferable that the glass transition temperature is not more than 150xc2x0 C., especially 40xc2x0 to 120xc2x0 C. (measured with DSC) from the viewpoint of giving a coating film being excellent in leveling property and appearance even at relatively low baking temperature.
The above-mentioned fluorine-containing copolymer having crosslinkable functional group not only gives excellent weather resistance, chemical resistance and stain removable property to an obtained coating film but also improves impact resistance and flexibility.
Then the curing agent which is another component of the thermosetting powder coating composition of the present invention is explained below.
A curing agent to be used may be selected optionally depending on kind of the above-mentioned crosslinkable functional group, a melt-kneading temperature at making a coating, a baling temperature, etc. In former thermosetting powder coating compositions containing a fluorine-containing copolymer, selection of a curing agent was difficult from the viewpoint of its compatibility with the copolymer, and kind of usable curing agent, particularly a combination with a resin was limited. According to the present invention, since crosslinkable functional group is introduced into the above-mentioned fluorine-containing copolymer, kind and combination of usable curing agent can be extended.
Examples of the usable curing agent are, for instance, epoxy or glycidyl compounds such as alicyclic epoxy resin, GMA acryl, aliphatic oxysilane, triglycidyl isocyanurate (TGIC), diglycidyl terephthalate, diglycidyl p-hydroxybenzoate, spiroglycol diglycidylether and hydantoin compounds; isophorone diisocyanate, tolylene diisocyanate, xylilene diisocyanate, 4,4xe2x80x2-diphenylmethane diisocyanate, hexamethylene diisocyanate, dimers thereof and blocked isocyanates obtained by blocking an isocyanate group of alcohol-modified polyisocyanate with a blocking agent (for example, xcex5-caprolactam, phenol, benzyl alcohol, methyl ethyl ketone oxime, etc.); polybasic acid curing agent such as xcex2-hydroxyalkylamide; polycarboxylic acids, e.g. aliphatic dibasic acids such as fumaric acid, succinic acid, adipic acid, azelaic acid, sebacic acid and dodecandioic acid (DDA) and acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; tetramethoxymethylglycoluryl, isocyanate -modified silane coupling agent, and other curing agents described in JP-B-6-104792, JP-A-7-188587 and JP-A-1-103670.
Among them, particularly from the viewpoint of compatibility with the crosslinkable functional group in the fluorine-containing copolymer (A), preferred combinations are as follows.
(1) Crosslinkable functional group: Hydroxyl group Curing agent: Blocked isocyanate, polyurethodione
(2) Crosslinkable functional group: Carboxyl group Curing agent: Triglycidyl isocyanurate, xcex2-hydroxyalkylamide, GMA acryl
(3) Crosslinkable functional group: Glycidyl group Curing agent: Aliphatic dibasic acid
It is preferable that an amount of the curing agent is from 0.1 to 1.2 equivalents, especially 0.5 to 1.0 equivalent to an amount of functional group contained in the fluorine-containing copolymer (A). When less than 0.1 equivalent, an effect of improvement by crosslinking in crack resistance at bending and impact resistance is not sufficient and water resistance is also lowered. When more than 1.2 equivalents, it results in lowering of appearance of a coating film.
In addition to the curing agent, a curing catalyst may be blended. Examples of the curing catalyst are, for instance, quaternary ammonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium iodide; quaternary phosphonium salts such as ethyltriphenylphosphonium acetate; phosphines such as triphenylphosphine; imidazoles such as 2-methylimidazole; organotin compounds such as dibutyltindilaurate and stannous octanoate; methyltolylsulfoneimide and stannous methanesulfonate, and the like. The curing catalyst may be blended in an amount of from about 0.1 part (part by weight, hereinafter the same) to about 3 parts to 100 parts of the fluorine-containing copolymer (A).
In addition to those additives, to the powder coating composition of the present invention may be blended various additives usually added in the field of paints, in an amount not lowering an effect of the present invention. Examples of such other additives are a pigment, extended pigment, flow control agent, antioxidant, thermal deterioration preventive agent, ultraviolet ray absorber, foaming inhibiting agent, flatting control agent, defoaming agent, electric charge control agent, antistatic agent, and the like.
Since a coating film formed with the fluorine-containing copolymer (A) of the present invention is transparent, various kinds of pigments can be used. For example, there are organic pigments such as condensed azo compounds, isoindolinone, quinacridone, diketopyrrolopyrol, anthraquinone, dioxazine and various organometal complexes; inorganic pigments such as titanium oxide (Preferred are one having rutile-type structure, and further preferable are alumina-treated, silica-treated or zirconia-treated titanium oxides), red iron oxide, yellow iron oxide, black iron oxide, carbon, chromium oxide, lead chromate, white lead and molybdenum orange; metal powders such as aluminum powder and stainless steel powder; and the like. Among them, inorganic pigments are preferred from the viewpoint of weather resistance which is one of the features of the present invention, particularly to maintain a gloss retention ratio and inhibit fading of color. A preferred content of the pigment is not more than 80 parts on the basis of 100 parts of the resin.
Examples of the extended pigment are, for instance, talc, silica, calcium carbonate, barium sulfate, mica, diatomaceous silica, asbestos, basic silicate, and the like.
Examples of the flow control agent are, for instance, acrylate polymers such as polylauryl acrylate, polybutyl acrylate and poly-2-ethylexyl acrylate; ester of polyethylene glycol and perfluorocarboxylic acid and fluorine-containing polymers having a low melting point such as VdF/TFE/HFP copolymer (excluding VdF polymers having crosslinkable functional group); silicone polymers such as polydimethylsiloxane and polymethylphenylsiloxane; and the like.
Then the process for preparing the powder coating composition of the present invention is explained below. As mentioned above, one of the features of the composition of the present invention is such that coating defects attributable to contamination are hard to arise when changing to or from a powder coating of other resin on a powder coating line.
The preparation process comprises the basic steps such as a pre-pulverizing step, dry blending step, melt-kneading step, pulverizing step and classifying step. (Pre-pulverizing step)
As mentioned above, the fluorine-containing copolymer having crosslinkable functional group can be obtained in various forms such as powder, flake, bulk, and the like. In order to obtain good mixing in the following dry blending step, the copolymers are formed into pellets of not more than 5 mm or pulverized into an average particle size of about 50 xcexcm to about 100 xcexcm. (Dry blending step)
The fluorine-containing copolymer having crosslinkable functional group in the form of powder or pellet, curing agent, curing catalyst and additives such as a pigment are dry-blended. A mixer to be used is usually a high speed mixer, low speed mixer or Henschel mixer. If a temperature inside the mixer is elevated too high, a reaction of the crosslinkable functional group with the curing agent advances. Therefore it is preferable that the inside temperature is maintained at a temperature of not more than 80xc2x0 C. by controlling time and mixer temperature.
The above-mentioned dry-blended product is put in a melt-kneader, melted at a temperature of not less than a melting point or Tg of the fluorine-containing copolymer (A) to knead sufficiently, and then extruded in the form of sheet. In that case, an extruder which is high in productivity in continuous production is used preferably. Examples of usual melt-kneader are a single screw extruding kneader, two screw extruding kneader, heating kneader and heating roll. A melt-kneading temperature and time are 80xc2x0 to 120xc2x0 C. and usually several tens of seconds, respectively so that the reaction of the functional group in the resin and the curing agent does not advance too much.
The sheet melt-extruded in a specified form is, after cooling and solidifying, roughly pulverized into chips of about 5 mm to about 15 mm and then finely pulverized. In that case, it is preferable that the pulverizer is maintained at a constant temperature with very low temperature pulverizing, air-cooling or water-cooling means. As the pulverizer, a high speed impact pulverizer, high speed pin type pulverizer, or the like is used preferably.
The finely pulverized powder is classified with a centrifugal classifier, blower type sieving machine, sieve shaking machine, or the like. A narrow particle size distribution is preferable. It is preferable that an average particle size of the powder coating composition is from 1 to 100 xcexcm, especially 10 to 50 xcexcm. When less than 1 xcexcm it is difficult to control a coating thickness because the particles are subject to electrostatic repulsion, and there occur problems with lowering of a coating efficiency due to lowering of collecting efficiency with a cyclone in case of recycling and also lowering of safety workability due to permeation through a protection mask. When more than 100 xcexcm, leveling property is lowered, thereby causing problems that appearance of a coating film becomes poor and coating thin cannot be carried out. An average particle size is determined by a desired coating thickness. For example, in case of a coating thickness of about 40 xcexcm to about 50 xcexcm, the average particle size is preferably 25 to 30 xcexcm. The smaller the average particle size is, the more the appearance of coating film is enhanced, and coating thin is possible, but a blockage occurs at spray-coating, thereby causing lowering of workability and adhesion of a coating.
The thermosetting powder coating composition of the present invention can be prepared in such a manner mentioned above.
The thermosetting powder coating composition of the present invention can be coated on various substrates by known applying methods. Then the coating film obtained by baking the coated film is excellent in its appearance such as smoothness and gloss, surface hardness, mechanical properties such as flexibility and impact resistance, adhesion to a substrate, weather resistance, stain-proofing property and water resistance.
Namely the present invention relates to the coated article obtained by coating the above-mentioned thermosetting powder coating composition on a substrate and then baking it for curing.
For coating, known coating methods can be employed. For example, there are electrostatic powder spray coating method, fluid bed coating method, electrostatic dip coating method, and the like. A coating thickness is usually in the range of from 20 to 100 xcexcm.
Then the coating film is baked. A baking temperature is not more than 200xc2x0 C., usually not less than 150xc2x0 C., preferably 160xc2x0 to 200xc2x0 C. A baking time is from 10 to 30 minutes, usually 15 to 20 minutes. At that baking temperature, the powder coating composition of the present invention exhibits excellent flowability and gives a smooth and uniform baked coating film.
The powder coating composition of the present invention is also excellent in adhesion to a substrate. The preferable substrate is one which has electric conductivity to enable electrostatic coating. Examples thereof are, for instance, various metal plates such as stainless steel plate, aluminum plate, steel plate and galvanized steel plate, and in addition, heat resistant engineering plastics such as polycarbonate, polyphenylene oxide, polyethylene terephthalate, polyether sulfone, polyamideimide and polyether ether ketone which are endowed with electric conductivity by dispersing a conductive carbon therein. It is preferable that those substrates are subjected to removal of rust by sand blasting or acid washing, baking, degreasing by washing with a solvent, with emulsion type cleaner or alkali, phosphating with zinc phosphate, calcium phosphate or iron phosphate, or chemical conversion treatment such as chromate treatment, alumite treatment or chromium phosphate treatment. In that case, though the coating composition of the present invention has enough adhesion to those substrates even in case of a single use thereof, as case demands, it is possible to carry out intermediate coating of zinc rich rust-preventive primer or various primers such as an epoxy resin and acrylic resin together. The intermediate coating may be applied in any form of solvent type coating, aqueous coating, powder coating or the like. It is preferable to apply in the form of powder coating from the viewpoint of workability in the present invention.
The coated article of the present invention is used for various applications. Non-restricted examples of the application are, for instance, applications described in xe2x80x9cHandbook of Powder Coating Techniquexe2x80x9d edited by Nippon Funtai Toso Kogyo Kyokai (1994), pp 169 to 173 such as construction and building material, electric communication device, vehicles, road materials, water and gas service materials, metal products, domestic appliances, machines, tools, measuring instruments, medical instruments, utensils for maintenance, agricultural materials, ships, sports and leisure products, and the like.
Then the present invention is explained by means of examples, but is not limited to them.
A 4-liter pressure resistant reactor equipped with a stirrer was charged with 1,000 ml of deionized water, and feeding of pressurized nitrogen and deairing were repeated to remove dissolved oxygen. Then the reactor was charged with 407 g of chlorofluoroethane (HCFC-141b), 15 g of perfluorobutenoic acid (PFBA) and 794 g of hexafluoropropane (HFP) successively. A pressure inside the reactor was increased up to 12 kgf/cm2 at 35xc2x0 C. with a monomer mixture of tetrafluoroethylene (TFE)/ethylene (ET) in a % by mole ratio of 82/18. Then the reactor was charged with 4 g of cyclohexane and 48 g of 25% flon 225 solution of isobutyryl peroxide, and the above-mentioned monomer mixture was supplied continuously so that the inside pressure became constant at 12 kgf/cm2. Every three hours after starting of the reaction, 8 g of 25% flon 225 solution of isobutyryl peroxide and 3 g of PFBA were added three times. After 12-hour reaction, the inside of the reactor was restored to normal temperature and normal pressure to terminate the reaction. After the obtained solid was washed and dehydrated, it was vacuum-dried at 80xc2x0 C. to give 133 g of TFE/HFP/ET/PFBA copolymer (white powder). Components, melting point (Tm), glass transition temperature (Tg), MFR and solubility in THF of the obtained copolymer were measured by the methods mentioned below. Melting point, glass transition temperature: A heat balance of 10 mg of VdF polymer was measured at a heat-up speed of 10xc2x0 C./min in a temperature range of xe2x88x9225xc2x0 C. to 200xc2x0 C. by using Thermal Analysis System (available from Perkin Elmer Co., Ltd.), and a top peak was assumed to be a melting point. Since the glass transition temperature (Tg) was detected as two variable polar points, it was obtained by a center point method.
MFR: Measurement was carried out under the conditions of 130xc2x0 C., a load of 2.1 kg and 10 minutes. In case of much flow, a period of time in which 20 g of resin flowed was measured and converted to an amount of resin flowing for 10 minutes.
Solubility in THF: 0.5 Gram of resin in the form of powder was put in 10 ml of THF at room temperature, and after allowed to stand for 72 hours, dissolving state was observed with naked eyes.
The results are shown in Table 1.
Polymerization was carried out in the same manner as in Preparation Example 1 except that monomers, amount of cyclohexane and polymerization time were changed as shown in Table 1. The same measurements as in Preparation Example 1 were carried out with respect to the obtained fluorine-containing copolymer. The results are shown in Table 1.
A 1-liter pressure resistant reactor was charged with 523 g of t-butanol (t-BA), 53 g of cyclohexyl vinyl ether (CHVE), 30 g of isobutyl vinyl ether (IBVE), 83 g of hydroxybutyl vinyl ether (HBVE), 3.3 g of potassium carbonate and 0.23 g of azobisisobutylonitrile, followed by solidifying with liquid nitrogen and deairing to remove dissolved oxygen. After that, 167 g of pressurized CTFE was introduced and the reactor was heated up to continue a reaction at 65xc2x0 C. over 10 hours. Then after cooling, residual monomer was distilled off, a solution was collected and a dispersion medium was distilled off at 60xc2x0 C. under reduced pressure to give a resin. This resin dissolved in THF. A glass transition temperature and MFR thereof were 24xc2x0 C. and 116, respectively.